Oxidizing organic compounds.



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Mice-i "QT-ONJEHEMAlN, lYlERMJlNY, ASSlGNGR TO l Ali-BWEHKE, VURM. Milli-STEEL LUCIUS 8c ERll -NlNG, 0F HUCHS'LP oxioszine oeennic 'GQMPQUNDm ereoimcnmon forming; part of Letters Petent No 757,136, deiid April 12, 1994.. Application filed September 1802; Serial 122,128. (No specimens.) I

Ir; "all whom 2125 may con-earm- Be it known that I, lVlAR'IFIN Moose, Ph. 1)..

a hizen of the Empireof Germany, residing at liochshun-thelllaiu, level-any, have menlie-(l eel-min new and useful Improvements in {)xidizing lrge-uic Compounds, of which the following is e, specification.

The cxials of cerium derived iherefron'i have hitherto not. been used to oxidize organic substances, yet it is known that, for instance,

ceric salts are used in the manufeceure of uni:

lin-hlzicle Dingleflz Hil /i". Jim/m. 212, 187 4C/ 349.) In this case, however, the ce rium merely note as the ca-riiei' of oxygen in e manner lithlc elueiila-ijei'l uptiil now. {SCl1L1ll3Z, (I/ie'qi M]. Smile/luring),Men's, 3Auil.) It is further (lQBSCl'lljiEfil in literature that eerie salts are reduced y nitricecicl on addition of alcohol 5i'neiiirKrz uh, fi ccvirlbzwllfil; l. i8'tl6 ZU8) to cei'ous Belts, when the solution becomes discolored. I. have found tuni; cerile oxide end. CQRlLU sells are powerful OX'lCllZi 1 agents, which not only oxidize sic-celled reducing" egenlis, hut which ere equal sti'e .h to chromic acid and pohissiui'n perinarugnnnte and may he used with advantage as e suhssi tote in many respects.

In oxidizing organic substances by means of cerium compounds two methods may he The cerium, compounds to he conemployed. eidered is cupuhle of oxidizing organic sub- I 'e: cerium clioxid, the sac-celled ce- (a mixture of oxide of rare metels,) cell the salts derived the. from. he cerium (lioxiiil oithe cerite oxide are used in the form of a fine brown powder containing about sixt to seventy per cent. of (Ye /1:. it

' mined or regenen iteil from its compounds by hire.

heebinglin the air. Thus by heating cerium sulfates in e current-of an cerium dioxicl and suifuric eeid enhyllnil are obteinecl.

It is particularly remarkable that thecerite oxide, or 3e02, which by themselves are (lificultly or hardly soluble in acids, may readily he transformed into cerous' salts by aci tl in the presence of even little oxidizchle organic substances 21ml of; a rela-Jiveiy low tempere.

process may he illustrated by the following example: A flask provided with an agitator and reflux condenser containsone liter of sulfuric eciil of sixty-percent. strength and thirty grams of toluene. The mixture is heated to about 60 c eilsigraile, two hundred greme of cerium dioxid or its hydrate 8e09, Hi l of eixtyeeven-per-cent. strength being added in smell portions at this temper-chore while stirring. introducecl, the iemperehure slowly 1' iserl to about 90 centigrede. The reaction is co1npleie when the brown cerite oxids are transmefl into white sulfate. The products of oxiclulion thus formed and the still unchengezi toluene are then dietilled with steam.

phenylmethene and enthraquinone are also obtained in smell quantities. The manufacture of metwiolyialdeiiyde from mete-xylol is quite similar.

is understood that the proportions given in the examples may vary within Wide limits, and pure GeCh may be used for cerite oxiol.

The oxidation by means of ceric salts is illustrated by the following examples:

1. An equeous solution which contains in. four liters eight hundred grains of sulfuric acid and two huncli-edgreme of ceric sulfate is heated to about GO ccnt-igi-adc, whereupon the celculaieii quantity of enthrecene is slowly introduced with Silllfl'llg anl the temperature is gradually raised to ehout 35f centigrede.

As to the reaction of cerite oxicls the When ell cerium (llOXlLl is The toluene may he separated irom the bengcclcle vhycle formed by fractional distillation. olyh After a short time the Whole of the enthracene is changed into antlu'equinone end the cerium.

solution has become. colorless. The anthraquinone is filtered and washed and 1s readyto be further worked up.

2. Into a solution containing fifteen to twenty per cent. of sulfuric acid and three to live per cent. of ceric sulfate naphthalene is introduced and the whole is gradually heated. According to the concentration of the acid and the quantity of cerium salt, the reaction begins at 45 to 60 centigrade, which temperature it is preferable to-maintain The reaction is complete when the cerium-sulfate solution has become completely colorless.

unchanged naphthalene, napbthoquinone and phthalic acid are obtained, which are isolated in the usual manner.

3. The oxidation is more energetic if in the above examples a, more concentrated sulfuric acid is employed.

dioxid or cericsulfate is introduced into a ens-- If, for instance, cerium pension of anthracene in concentrated sulfu- 'ric acid, then an energetic reaction occurs already at about 259' centigrade." The mass assumes a dark color, while spontaneously evolving heat, and finally carbonizes, muchv sulfurousacid escaping thereby. The reaction maybe modified at will by changing the concentration of the acid and by regulating the temperature correspondingly.

In the above-cited examples other ceric salts may be used for ceric sulfatefor instance,

ceric' nitrate, ceric ammonia-nitrate, &,c. an addition of sulfuric acid not being then absolutely necessary. I

Besides some substantially as set forth.

For. the hydrocarbons mentioned in the 35 above examples may be substituted their wellknown readily-oxidizable substitution prod- 1 ucts--such as, for instance, their nitro, ,nitroso, sulfonic, oxy, and halogen substitution products.

The temperature, the proportionsof quantity, and current in the above-given examples may varywithin wide limits.

,Having thus described my invention, I

claim- 1. The herein-described process foroxidizing aromatic hydrocarbons and their substitutron products, which consists in causing ceric compounds to act on said aromatic compounds,

2. The herein-described process for oxidizing aromatic hydrocarbons and their substitution products, which consists in causing the oxide ofthe cerite gr up to act on said oxy compounds in presence of acids, substantially as set forth.

The herein-described process for oxidizing aromatic hydrocarbons and their substitutron products, which COIlSlStSlD caus ng QGIIC salts to act on said organic compounds, substantially as set forth. 

